Interpolymer, process for its preparation and adhesive of improved creep resistance containing the interpolymer

Abstract

Interpolymers are provided which are based upon the interpolymerization of a vinyl ester, a lower alpha olefin, optionally an alpha, beta ethylenically unsaturated carboxylic acid and a vinylcyclopropanedicarboxylate polyester oligomer or mixtures thereof. The interpolymers are particularly useful for formulating latex adhesives where they have been found to significantly improve the creep resistance properties thereof.

What is claimed is: 
     
       1. An interpolymer derived from the interpolymerization of (a) a vinyl ester;   (b) a lower alpha olefin; and   (c) a vinylcyclopropanedicarboxylate polyester oligomer or mixture thereof of the formula: ##STR7##  wherein R is a bivalent radical derived from a C 2-12  aliphatic diol, C 3-12  cycloaliphatic diol, C 8-10  aromatic diol or ether diol having from about 4 to about 60 carbon atoms and about 1 to about 30 ether moieties, n is an integer from about 1 to about 20 and X and Y are terminating groups.   
     
     
       2. The interpolymer of claim 1 which further comprises (d) an alpha, beta ethylenically unsaturated carboxylic acid. 
     
     
       3. The interpolymer of claim 1 wherein the vinyl ester is vinyl acetate. 
     
     
       4. The interpolymer of claim 2 wherein the alpha, beta ethylenically unsaturated carboxylic acid is acrylic acid or methacrylic acid. 
     
     
       5. The interpolymer of claim 1 wherein the lower alpha-olefin is ethylene. 
     
     
       6. The interpolymer of claim 1 wherein, in the vinylcyclopropanedicarboxylate polyester oligomer, X is hydroxy, alkoxy or the group -OROH, where R is a bivalent radical derived from a C 2-12  aliphatic diol, C 3-12  cycloaliphatic diol, C 8-20  aromatic diol or ether diol having 4 to 60 carbon atoms and 1 to about 30 ether moieties and Y is hydrogen or the radical ##STR8## where R 1  is hydrogen or a C 1-14  alkyl group. 
     
     
       7. The interpolymer of claim 1 wherein the vinylcyclopropanedicarboxylate polyester oligomer is a mixture of oligomers, the major part by weight of said mixture being made up of oligomers in which n is 1 to about 
     
     
       8. The interpolymer of claim 7 wherein in the vinylcyclopropanedicarboxylate polyester oligomer or mixture thereof, X is hydroxy, alkoxy or the group --OROH where R is a bivalent radical derived from C 2-12  aliphatic diol, C 3-12  cycloaliphatic diol, C 8-20  aromatic diol or ether diol having from about 4 to about 60 carbon atoms and about 1 to about 30 ether moieties and Y is hydrogen or the radical ##STR9## where R 1  is hydrogen or a C 1-4  alkyl group. 
     
     
       9. The interpolymer of claim 8 wherein the vinylcycylopropanedicarboxylate polyester oligomer or mixture thereof has an average molecular weight from about 200 to about 15,000 and a 24° C. viscosity of about 0.2 to about 200 poise. 
     
     
       10. The interpolymer of claim 9 wherein the average molecular weight of the vinylcyclopropanedicarboxylate polyester oligomer or mixture thereof is about 300 to about 6,000 and the viscosity is about 0.3 to about 150 poise. 
     
     
       11. The interpolymer of claim 1 wherein the vinylcyclopropanedicarboxylate polyester oligomer or mixture thereof is obtained by the reaction of 1-vinylcyclopropane2,2-dicarboxylic acid or C 1-4  alkyl ester thereof with a diol selected from the group consisting of C 2-12  aliphatic diol, C 3-12  cycloaliphatic diol, C 8-20  aromatic diol or ether diol having from 4 to about 60 carbon atoms and 1 to about 30 ether moieties, the respective reactants present in an equivalents ratio from about 2:1 to about 1:2. 
     
     
       12. The interpolymer of claim 11 wherein the equivalents ratio of the reactants is from about 1.3:1 to about 1:1.3. 
     
     
       13. The interpolymer of claim 1 wherein the vinyl ester is present from about 40 to about 95 weight percent of the total charge. 
     
     
       14. The interpolymer of claim 1 wherein lower alpha olefin is present from about 5 to about 60 weight percent of the total charge. 
     
     
       15. The interpolymer of claim 2 wherein the alpha, beta ethylenically unsaturated carboxylic acid is present from about 0.5 to about 5.0 weight percent of the total charge. 
     
     
       16. The interpolymer of claim 1 wherein the vinylcyclopropanedicarboxylate polyester oligomer is present from about 0.1 to about 1.0 weight percent of the total charge. 
     
     
       17. A latex containing the interpolymer of claim 1. 
     
     
       18. A latex containing the interpolymer of claim 2. 
     
     
       19. A latex adhesive composition of improved creep resistance, containing an interpolymer of claim 1. 
     
     
       20. A latex adhesive composition of improved creep resistance containing an interpolymer of claim 2. 
     
     
       21. A process for preparing an interpolymer latex which possesses at least about 60 weight percent of combined vinyl acetate from: (a) vinyl ester in an amount representing from about 40 weight percent to about 95 weight percent of the total charge;   (b) a lower alpha olefin representing from about 5 to about 60 weight percent of the total charge; and   (c) vinylcyclopropanedicarboxylate polyester oligomer or mixture thereof of the formula: ##STR10##  representing from about 0.1 to about 1.0 weight percent of the total charge which comprises polymerizing in a single reaction stage at least 10 weight percent of the total vinyl ester monomer (a) under an ethylene pressure of about 100 to about 1,000 psi in an aqueous emulsion reaction medium containing a polymerization catalyst, and thereafter polymerizing in said reaction, the remaining portion of the total vinyl ester monomer (a) together with the lower alpha olefin (b) and the vinylcyclopropanedicarboxylate polyester oligomer (c) in the reaction medium containing additional catalyst, if needed, polymerization being continued substantially to completion.   
     
     
       22. The process of claim 21 which further comprises the addition of (d) an alpha, beta ethylenically unsaturated carboxylic acid in an amount of from about 0.5 to about 5.0 weight percent of the total, charge. 
     
     
       23. The process of claim 21 wherein the lower alpha-olefin is ethylene. 
     
     
       24. The process of claim 21 in which one or more other ethylenically unsaturated monomers copolymerizable with the vinyl ester (a), the ethylenically unsaturated monomer (b), the vinylcyclopropanedicarboxylate polyester oligomer or mixtures thereof (c), and the alpha, beta ethylenically unsaturated carboxylic acid (d), present in an amount of up to about 10 weight percent of the total charge is added at the commencement of, or during, polymerization. 
     
     
       25. The process of claim 21 in which less than about 60 weight percent of total vinyl ester monomer present is initially added to the rection medium with the balance thereof being sequentially added to the reaction medium with monomer (b), vinylcyclopropanedicarboxylate polyester oligomer or mixtures thereof (c) and the alpha, beta ethylenically unsaturated carboxylic acid. 
     
     
       26. The process of claim 21 in which the reaction medium additionally contains at least one surface active agent selected from the group consisting of nonionic surface active agents, anionic surface active agents, and mixtures thereof. 
     
     
       27. The process of claim 21 in which the reaction medium additionally contains a protective colloid. 
     
     
       28. The process of claim 21 wherein which the reaction medium additonally contains an alkaline buffering agent. 
     
     
       29. The process of claim 21 wherein the vinyl ester (a), the ethylenically unsaturated monomer (b) and the vinylcyclopropanedicarboxylate polyester oligomer (c) can be introduced sequentially or simultaneously before or during the interpolymerization reaction. 
     
     
       30. The interpolymer latex prepared by the process of claim 21. 
     
     
       31. The interpolymer latex prepared by the process of claim 22. 
     
     
       32. An adhesive composition of improved creep resistance containing an interpolymer latex prepared by the process of claim 21. 
     
     
       33. The process of claim 21 wherein the ethylene pressure is about 300 to about 600 psi. 
     
     
       34. The process of claim 25 wherein the surface active agent is present up to about 3 weight percent of the total charge. 
     
     
       35. The process of claim 26 wherein the surface active agent is present from about 0.1 to about 1.0 weight percent of the total charge. 
     
     
       36. The process of claim 21 wherein the polymerization temperature is about 10° to about 95° C. 
     
     
       37. The process of claim 25 wherein the buffer is present from about 0.01 to about 1.0 weight percent of the total charge. 
     
     
       38. The process of claim 21 in which the reaction medium additionally contains a protective colloid in an amount from about 0.01 to about 5.0% by weight of the total charge.